CN106753326A - M:ZnSe/ZnSe/ZnS structure quantum point preparation methods - Google Patents
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Abstract
The invention belongs to quantum dot preparation field, it is related to a kind of M:ZnSe/ZnSe/ZnS nuclear shell structure quantum point preparation methods：Under an inert atmosphere, by Microwave-assisted firing device, the M of metal ion mixing is gone out using solvent-thermal process:ZnSe quantum dots, room temperature is down to by reaction temperature, and zinc source and organic surface ligand solution are injected in reaction solution, in M:ZnSe quantum dots outer layer forms ZnSe shells, adjusts microwave reaction temperature, injects sodium sulfide solution, forms M:The quantum dot of ZnSe/ZnSe/ZnS core shell structures.By the quantum dot powder that washing, centrifugation are obtained, while quantum dot forms quantum dot ink in being scattered in the solvent of isopropanol, ethanol, ethylene glycol and deionized water composition.The inventive method temperature control is accurate, quantum dot size is homogeneous, quantum dot surface defect is few and production efficiency is high, and three-layer nuclear shell structure quantum dot has fluorescence quantum yield higher.
Description
Technical field
The present invention principally falls into quantum dot field, and in particular to M:ZnSe/ZnSe/ZnS structure quantum point preparation methods.
Background technology
Quantum dot (Quantum Dots) is also referred to as semiconductor nano, be a kind of particle radius be less than or close to swash
Sub- Bohr radius, the semi-conductor nano particles being generally made up of II-VI or III-group Ⅴ element.When quantum dot is subject to certain wavelength
After the light of energy is excited, the certain energy of Electron absorption in its valence band transits to conduction band, the electronics as free movement, with
Free hole in valence band turns into electron-hole pair, be now in excitation state electronics can to low energy order transition, and with light
Form emittance, sends fluorescence.The emission spectrum of different quantum dots is different, and produced color is also different.Quantum dot due to
Its luminous efficiency is high, band gap continuously adjustabe and the property such as chemical stability is good, in fluorescence probe, solar cell, light-emitting diodes
The field extensive uses such as pipe (Q-LED).
Using quantum dot prepare Q-LED efficiencies are high, low cost, good stability and easy processing, in total colouring and solid-state
The application aspects such as illumination have great potentiality.(Colvin V L, Schlamp the M C, Alivisatos such as Colvin in 1994
A P.Nature,1994,370:354-357.) Q-LED is reported using CdSe Colloidal Quantum Dots for the first time.Then, Sun etc.
(SunQ J,Wang Y A.Nature.Photonics,2007,1:717) by the optimization to quantum dot layer thickness, make it is red,
Orange, the highest of the Q-LED of yellow and green light and can reach 9064,3200,4470 and 3700cd/m respectively2But, device
Less stable.Then, increasing people has started to study all components of Q-LED and achieved progress.In view of
Colloidal Quantum Dots solution machinability, Q-LED will it is main using Colloidal Quantum Dots by the technique of printing or spraying realize it is low into
Originally, the LED productions of large area.
At present, wide variety of is the quantum dot containing Cd, such as CdTe, CdSe class luminescent quantum dot, these quantum dots tool
There is luminous efficiency very high, but there is also many shortcomings, because they are heavy metal ion, with bio-toxicity, its application is received
Limitation is arrived.The ZnSe quantum dots of broad stopband due to its good monochromaticjty, fluorescence continuously adjustabe in bluish violet light emitting region,
And nontoxicity has broad application prospects in quantum dot blue light diode.But ZnSe quantum dots are made due to the problem of its energy level
The injection in hole becomes poorly efficient, causes fluorescence quantum yield low, and then causes luminous efficiency low.Therefore, high-quality indigo plant is synthesized
Light quanta point is most important for preparing high performance quantum dot blue light-emitting diode.
The technology of preparing of ZnSe quantum dots mainly includes metal organic solvent method, chemical coprecipitation, microwave process for synthesizing, molten
Glue-gel method and molecular beam epitaxy etc..Metal organic solvent method is synthesizing nano-particle method the most frequently used at present, but
Metallo-organic compound is expensive, and toxicity is big, easily pollutes environment, is detrimental to health, it is impossible to extensive use.Chemical coprecipitation
Shallow lake method has reaction temperature low, the low advantage of simple to operate, cost of material, but a disadvantage is that the quantum dot purity for preparing is relatively low,
Need further to modify quantum dot.Traditional heating mode be according to heat transfer, convection current and radiation theory make heat from
Outside reaches reaction solution, and heat always from outward appearance to inner essence heated by transmission, and temperature ladder is inevitably present in reaction solution
Degree, therefore heating is uneven, hot-spot occurs, causes quantum dot size to be distributed wide.The mode penetrability of heating using microwave is strong, plus
Thermal velocity is fast, homogeneous heating, more can accurate temperature controlling so that quantum dot size distribution narrow, its band gap is adjusted exactly and is had
Beneficial to industrialization, the development of automation.
The content of the invention
Regarding to the issue above, the present invention provides a kind of M:The preparation method of ZnSe/ZnSe/ZnS nuclear shell structure quantum points.This
Three-layer nuclear shell structure quantum dot is planted, broad-band gap ZnS and ZnSe two-layer shell not only reduces narrow band gap M:The surface of ZnSe quantum dots
Defect, the exciton that can also improve quantum dot is excited and exciton yield, and then improvement fluorescence quantum yield.
The present invention is achieved by the following technical solutions：
M:ZnSe/ZnSe/ZnS structure quantum point preparation methods, the described method comprises the following steps：
(1) under an inert atmosphere, selenium powder Se and sodium borohydride NaBH4Deionized water is dissolved in, Se sources presoma is obtained molten
Liquid；
(2) zinc acetate Zn (CH3COO)2With Doped ions Cu2+、Mn2+、Al3+Dissolving metal salts go to organic surface ligand
Deionized water solution, recycles NaOH NaOH to adjust solution PH to 6~7, obtains metal ions M:Zn precursor solutions；
(3) metal ions M:Zn precursor solutions are placed in microwave reaction device, carry out vacuumizing 10~40min, afterwards
Inert gas is passed through, the precursor solution of Se is then injected into metal ions M:In Zn precursor solutions, using heating using microwave,
Reaction solution is heated to 75~95 DEG C from room temperature, 1~3h is incubated；
(4) reaction temperature is down to room temperature, is then injected into Zn (CH3COO)2With the deionized water solution of organic surface ligand,
75~95 DEG C are warmed up to again, are incubated 30~90min；
(5) reaction temperature is down to 50~60 DEG C, afterwards using the PH of NaOH regulation reaction solutions to 11~13, then is heated up
To 70~85 DEG C, Na is now injected in reaction solution2S deionized water solutions, after 30~90min of insulation, are cooled to room temperature, obtain
Obtain M:The quantum dot solution of ZnSe/ZnSe/ZnS three-layer nuclear shell structures；
(6) quantum dot solution of gained is washed, is centrifuged and dried, obtained quantum dot powder；
Wherein, the M includes Cu, Mn, Al；
M in metal ion precursor solution:The mol ratio of Zn is 1:30~1:5；
Se sources precursor solution：Metal ions M:Zn precursor solutions：Zinc source：The molar concentration rate of sodium sulfide solution is 1:
0.5:1:0.5；
The molar concentration rate of the metal ion and organic surface ligand solution is 1：9~10.
Further, Se sources precursor solution, metal ions M:Zn precursor solutions, zinc source, sodium sulfide solution mole
Concentration is 0.02~0.1M；The molar concentration of organic surface ligand solution is 0.2~0.9M.
Further, organic surface ligand includes 3- mercaptopropionic acids, TGA, glutathione or cysteine.
A kind of quantum dot printing ink preparation method, using the M obtained by the preparation of claim 1-8 either method:ZnSe/
ZnSe/ZnS structure quantum points prepare printing ink, by the M:ZnSe/ZnSe/ZnS structure quantum points be distributed to by isopropanol,
Ethanol, ethylene glycol and deionized water are according to volume ratio 1:1:1:In the solvent of 1 composition, the M of 0.05~0.5M of molar concentration is formed:
ZnSe/ZnSe/ZnS quantum dot inks.
Advantageous Effects of the invention：1) this three-layer nuclear shell structure quantum dot, broad-band gap ZnS and ZnSe two-layer shell
Not only reduce narrow band gap M:The surface defect of ZnSe quantum dots, can also promote exciton to excite and exciton yield, and then raising amount
The fluorescence quantum yield of son point；
2) microwave reaction has heating, cooling speed fast, and temperature control is accurate, is conducive to acquisition size uniformity, surface to lack
Few high-quality quantum dot is fallen into, and the method production efficiency is high.
Brief description of the drawings
Fig. 1 is M:The structural representation of ZnSe/ZnSe/ZnS three-layer nuclear shell structure quantum dots：
Fig. 2 is the Mn of Mn doping prepared by the inventive method:The fluorogram of ZnSe/ZnSe/ZnS quantum dots；
Fig. 3 is the Cu of Cu doping prepared by the inventive method:The fluorogram of ZnSe/ZnSe/ZnS quantum dots；
In figure：1、M:ZnSe quantum dots；2nd, ZnSe quantum dots；3rd, ZnS quantum dot.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is explained in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, and
It is not used in the restriction present invention.
Conversely, the present invention covers any replacement done in spirit and scope of the invention being defined by the claims, repaiies
Change, equivalent method and scheme.Further, in order that the public has a better understanding to the present invention, below to of the invention thin
It is detailed to describe some specific detail sections in section description.Part without these details for a person skilled in the art
Description can also completely understand the present invention.
Embodiment 1
M:ZnSe/ZnSe/ZnS structure quantum point preparation methods, comprise the following steps that：
A) under an inert atmosphere, by Se powder and NaBH4It is dissolved into deionized water, obtains Se sources precursor solution；
b)Zn(CH3COO)2With Mn (CH3COO)2It is dissolved into the deionized water solution of organic surface ligand MPA, by drop
Plus NaOH solution regulation PH to 6, obtain Mn:Zn sources precursor solution；
C) container that will fill the precursor solution obtained in b is positioned in microwave reaction device, is then vacuumized
40min, then inert gas is passed through, hereafter, the precursor solution of Se is injected into Mn:In the precursor solution of Zn sources, using microwave
Heating, is heated to 75 DEG C, is incubated 3h；
D) reaction temperature is down to room temperature, reinjects Zn (CH3COO)2With the MPA aqueous solution, then 75 DEG C are warming up to, insulation
90min；
E) reaction temperature is down to 50 DEG C, the PH of reaction solution is adjusted to 11, be warming up to 70 DEG C and be subsequently adding Na2S water
Solution, after insulation 90min, is cooled to room temperature, obtains Mn:The quantum dot of ZnSe/ZnSe/ZnS core shell structures, takes the component such as a small amount of
The quantum dot that obtains of different soaking times carry out optical performance test；
F) quantum dot solution of gained washed, be centrifuged, obtained quantum dot powder.
Further, M:ZnSe/ZnSe/ZnS structure quantum point ink-manufacturing methods：
G) quantum dot of gained is distributed to by isopropanol, ethanol, ethylene glycol and deionized water according to volume ratio 1:1:1:1
In the solvent of composition, Mn is formed:ZnSe/ZnSe/ZnS quantum dot inks.
Wherein, the Mn that various concentrations are obtained:The optical property of ZnSe/ZnSe/ZnS quantum dots lists table 1 in.
The Mn of table 1:The influence of ZnSe/ZnSe/ZnS quantum dot optical properties
Embodiment 2
M:ZnSe/ZnSe/ZnS structure quantum point preparation methods, comprise the following steps that：
A) under an inert atmosphere, by Se powder and NaBH4It is dissolved into deionized water, obtains Se sources precursor solution；
b)Zn(CH3COO)2With Mn (CH3COO)2It is dissolved into the deionized water solution of organic surface ligand TGA, by drop
Plus NaOH solution regulation PH to 7, obtain Mn:Zn sources precursor solution；
C) container that will fill the precursor solution obtained in b is positioned in microwave reaction device, is then vacuumized
30min, then inert gas is passed through, hereafter, the precursor solution of Se is injected into Mn:In the precursor solution of Zn sources, using microwave
Heating, is heated to 95 DEG C, is incubated 1h；
D) reaction temperature is down to room temperature, reinjects Zn (CH3COO)2With the TGA aqueous solution, then 95 DEG C are warming up to, insulation
30min；
E) reaction temperature is down to 60 DEG C, the PH of reaction solution is adjusted to 13, be warming up to 85 DEG C and be subsequently adding Na2S water
Solution, after insulation 30min, is cooled to room temperature, obtains Mn:The quantum dot of ZnSe/ZnSe/ZnS core shell structures, takes the component such as a small amount of
The quantum dot that obtains of different soaking times carry out optical performance test；
F) quantum dot solution of gained washed, be centrifuged, obtained quantum dot powder；
Further, M:ZnSe/ZnSe/ZnS structure quantum point ink-manufacturing methods：
G) quantum dot of gained is distributed to by isopropanol, ethanol, ethylene glycol and deionized water according to volume ratio 1:1:1:1
In the solvent of composition, Mn is formed:ZnSe/ZnSe/ZnS quantum dot inks.
Wherein, the Mn that various concentrations are obtained:The optical property of ZnSe/ZnSe/ZnS quantum dots lists table 2 in.
The Mn of table 2:The influence of ZnSe/ZnSe/ZnS quantum dot optical properties
Embodiment 3
M:ZnSe/ZnSe/ZnS structure quantum point preparation methods, comprise the following steps that：
A) under an inert atmosphere, by Se powder and NaBH4It is dissolved into deionized water, obtains Se sources precursor solution；
b)Zn(CH3COO)2With Mn (CH3COO)2It is dissolved into the deionized water solution of organic surface ligand GSH, by drop
Plus NaOH solution regulation PH to 6.5, obtain Mn:Zn sources precursor solution；
C) container that will fill the precursor solution obtained in b is positioned in microwave reaction device, is then vacuumized
20min, then inert gas is passed through, hereafter, the precursor solution of Se is injected into Mn:In the precursor solution of Zn sources, using microwave
Heating, is heated to 85 DEG C, is incubated 2h；
D) reaction temperature is down to room temperature, reinjects Zn (CH3COO)2With the GSH aqueous solution, then 85 DEG C are warming up to, insulation
60min；
E) reaction temperature is down to 55 DEG C, the PH of reaction solution is adjusted to 12, be warming up to 80 DEG C and be subsequently adding Na2S water
Solution, after insulation 60min, is cooled to room temperature, obtains Mn:The quantum dot of ZnSe/ZnSe/ZnS core shell structures, takes the component such as a small amount of
The quantum dot that obtains of different soaking times carry out optical performance test；
F) quantum dot solution of gained washed, be centrifuged, obtained quantum dot powder；
Further, M:ZnSe/ZnSe/ZnS structure quantum point ink-manufacturing methods：
G) quantum dot of gained is distributed to by isopropanol, ethanol, ethylene glycol and deionized water according to volume ratio 1:1:1:1
In the solvent of composition, Mn is formed:ZnSe/ZnSe/ZnS quantum dot inks.
Wherein, the Mn that various concentrations are obtained:The optical property of ZnSe/ZnSe/ZnS quantum dots lists table 3 in.
The Mn of table 3:The influence of ZnSe/ZnSe/ZnS quantum dot optical properties
Embodiment 4
M:ZnSe/ZnSe/ZnS structure quantum point preparation methods, comprise the following steps that：
A) under an inert atmosphere, by Se powder and NaBH4It is dissolved into deionized water, obtains Se sources precursor solution；
b)Zn(CH3COO)2With Cu (CH3COO)2It is dissolved into the deionized water solution of organic surface ligand MPA, by drop
Plus NaOH solution regulation PH to 6, obtain Cu:Zn sources precursor solution；
C) container that will fill the precursor solution obtained in b is positioned in microwave reaction device, is then vacuumized
40min, then inert gas is passed through, hereafter, the precursor solution of Se is injected into Cu:In the precursor solution of Zn sources, using microwave
Heating, is heated to 75 DEG C, is incubated 3h；
D) reaction temperature is down to room temperature, reinjects Zn (CH3COO)2With the MPA aqueous solution, then 75 DEG C are warming up to, insulation
90min；
E) reaction temperature is down to 50 DEG C, the PH of reaction solution is adjusted to 11, be warming up to 70 DEG C and be subsequently adding Na2S water
Solution, after insulation 90min, is cooled to room temperature, obtains Cu:The quantum dot of ZnSe/ZnSe/ZnS core shell structures, takes the component such as a small amount of
The quantum dot that obtains of different soaking times carry out optical performance test；
F) quantum dot solution of gained washed, be centrifuged, obtained quantum dot powder；
Wherein, the Cu that various concentrations are obtained:The optical property of ZnSe/ZnSe/ZnS quantum dots lists table 4 in.
The Cu of table 4:The influence of ZnSe/ZnSe/ZnS quantum dot optical properties
Further, M:ZnSe/ZnSe/ZnS structure quantum point ink-manufacturing methods：
G) quantum dot of gained is distributed to by isopropanol, ethanol, ethylene glycol and deionized water according to volume ratio 1:1:1:1
In the solvent of composition, Cu is formed:ZnSe/ZnSe/ZnS quantum dot inks.
Embodiment 5
M:ZnSe/ZnSe/ZnS structure quantum point preparation methods, comprise the following steps that：
A) under an inert atmosphere, by Se powder and NaBH4It is dissolved into deionized water, obtains Se sources precursor solution；
b)Zn(CH3COO)2With Cu (CH3COO)2It is dissolved into the deionized water solution of organic surface ligand TGA, by drop
Plus NaOH solution regulation PH to 7, obtain Cu:Zn sources precursor solution；
C) container that will fill the precursor solution obtained in b is positioned in microwave reaction device, is then vacuumized
30min, then inert gas is passed through, hereafter, the precursor solution of Se is injected into Cu:In the precursor solution of Zn sources, using microwave
Heating, is heated to 95 DEG C, is incubated 1h；
D) reaction temperature is down to room temperature, reinjects Zn (CH3COO)2With the TGA aqueous solution, then 95 DEG C are warming up to, insulation
30min；
E) reaction temperature is down to 60 DEG C, the PH of reaction solution is adjusted to 13, be warming up to 85 DEG C and be subsequently adding Na2S water
Solution, after insulation 30min, is cooled to room temperature, obtains Cu:The quantum dot of ZnSe/ZnSe/ZnS core shell structures, takes the component such as a small amount of
The quantum dot that obtains of different soaking times carry out optical performance test；
F) quantum dot solution of gained washed, be centrifuged, obtained quantum dot powder；
Further, M:ZnSe/ZnSe/ZnS structure quantum point ink-manufacturing methods：
G) quantum dot of gained is distributed to by isopropanol, ethanol, ethylene glycol and deionized water according to volume ratio 1:1:1:1
In the solvent of composition, Cu is formed:ZnSe/ZnSe/ZnS quantum dot inks.Wherein, the Cu that various concentrations are obtained:ZnSe/ZnSe/
The optical property of ZnS quantum dot lists table 5 in.
The Cu of table 5:The influence of ZnSe/ZnSe/ZnS quantum dot optical properties
Embodiment 6
M:ZnSe/ZnSe/ZnS structure quantum point preparation methods, comprise the following steps that：
A) under an inert atmosphere, by Se powder and NaBH4It is dissolved into deionized water, obtains Se sources precursor solution；
b)Zn(CH3COO)2With Cu (CH3COO)2It is dissolved into the deionized water solution of organic surface ligand GSH, by drop
Plus NaOH solution regulation PH to 6.5, obtain Cu:Zn sources precursor solution；
C) container that will fill the precursor solution obtained in b is positioned in microwave reaction device, is then vacuumized
20min, then inert gas is passed through, hereafter, the precursor solution of Se is injected into Cu:In the precursor solution of Zn sources, using microwave
Heating, is heated to 85 DEG C, is incubated 2h；
D) reaction temperature is down to room temperature, reinjects Zn (CH3COO)2With the GSH aqueous solution, then 85 DEG C are warming up to, insulation
60min；
E) reaction temperature is down to 55 DEG C, the PH of reaction solution is adjusted to 12, be warming up to 80 DEG C and be subsequently adding Na2S water
Solution, after insulation 60min, is cooled to room temperature, obtains Cu:The quantum dot of ZnSe/ZnSe/ZnS core shell structures, takes the component such as a small amount of
The quantum dot that obtains of different soaking times carry out optical performance test；
F) quantum dot solution of gained washed, be centrifuged, obtained quantum dot powder；
Further, M:ZnSe/ZnSe/ZnS structure quantum point ink-manufacturing methods：
G) quantum dot of gained is distributed to by isopropanol, ethanol, ethylene glycol and deionized water according to volume ratio 1:1:1:1
In the solvent of composition, Cu is formed:ZnSe/ZnSe/ZnS quantum dot inks.Wherein, the Cu that various concentrations are obtained:ZnSe/ZnSe/
The optical property of ZnS quantum dot lists table 6 in.
The Cu of table 6:The influence of ZnSe/ZnSe/ZnS quantum dot optical properties
Embodiment 7
M:ZnSe/ZnSe/ZnS structure quantum point preparation methods, comprise the following steps that：
A) under an inert atmosphere, by Se powder and NaBH4It is dissolved into deionized water, obtains Se sources precursor solution；
b)Zn(CH3COO)2With Al (CH3COO)3It is dissolved into the deionized water solution of organic surface ligand MPA, by drop
Plus NaOH solution regulation PH to 6, obtain Al:Zn sources precursor solution；
C) container that will fill the precursor solution obtained in b is positioned in microwave reaction device, is then vacuumized
40min, then inert gas is passed through, hereafter, the precursor solution of Se is injected into Al:In the precursor solution of Zn sources, using microwave
Heating, is heated to 75 DEG C, is incubated 3h；
D) reaction temperature is down to room temperature, reinjects Zn (CH3COO)2With the MPA aqueous solution, then 75 DEG C are warming up to, insulation
90min；
E) reaction temperature is down to 50 DEG C, the PH of reaction solution is adjusted to 11, be warming up to 70 DEG C and be subsequently adding Na2S water
Solution, after insulation 90min, is cooled to room temperature, obtains Al:The quantum dot of ZnSe/ZnSe/ZnS core shell structures, takes the component such as a small amount of
The quantum dot that obtains of different soaking times carry out optical performance test；
F) quantum dot solution of gained washed, be centrifuged, obtained quantum dot powder；
Further, M:ZnSe/ZnSe/ZnS structure quantum point ink-manufacturing methods：
G) quantum dot of gained is distributed to by isopropanol, ethanol, ethylene glycol and deionized water according to volume ratio 1:1:1:1
In the solvent of composition, Al is formed:ZnSe/ZnSe/ZnS quantum dot inks.
Wherein, the Al that various concentrations are obtained:The optical property of ZnSe/ZnSe/ZnS quantum dots lists table 7 in.
The Al of table 7:The influence of ZnSe/ZnSe/ZnS quantum dot optical properties
Embodiment 8
M:ZnSe/ZnSe/ZnS structure quantum point preparation methods, comprise the following steps that：
A) under an inert atmosphere, by Se powder and NaBH4It is dissolved into deionized water, obtains Se sources precursor solution；
b)Zn(CH3COO)2With Al (CH3COO)3It is dissolved into the deionized water solution of organic surface ligand TGA, by drop
Plus NaOH solution regulation PH to 7, obtain Al:Zn sources precursor solution；
C) container that will fill the precursor solution obtained in b is positioned in microwave reaction device, is then vacuumized
30min, then inert gas is passed through, hereafter, the precursor solution of Se is injected into Al:In the precursor solution of Zn sources, using microwave
Heating, is heated to 95 DEG C, is incubated 1h；
D) reaction temperature is down to room temperature, reinjects Zn (CH3COO)2With the TGA aqueous solution, then 95 DEG C are warming up to, insulation
30min；
E) reaction temperature is down to 60 DEG C, the PH of reaction solution is adjusted to 13, be warming up to 85 DEG C and be subsequently adding Na2S water
Solution, after insulation 30min, is cooled to room temperature, obtains Al:The quantum dot of ZnSe/ZnSe/ZnS core shell structures, takes the component such as a small amount of
The quantum dot that obtains of different soaking times carry out optical performance test；
F) quantum dot solution of gained washed, be centrifuged, obtained quantum dot powder；
Further, M:ZnSe/ZnSe/ZnS structure quantum point ink-manufacturing methods：
G) quantum dot of gained is distributed to by isopropanol, ethanol, ethylene glycol and deionized water according to volume ratio 1:1:1:1
In the solvent of composition, Al is formed:ZnSe/ZnSe/ZnS quantum dot inks.
Wherein, the Al that various concentrations are obtained:The optical property of ZnSe/ZnSe/ZnS quantum dots lists table 8 in.
The Al of table 8:The influence of ZnSe/ZnSe/ZnS quantum dot optical properties
Embodiment 9
M:ZnSe/ZnSe/ZnS structure quantum point preparation methods, comprise the following steps that：
A) under an inert atmosphere, by Se powder and NaBH4It is dissolved into deionized water, obtains Se sources precursor solution；
b)Zn(CH3COO)2With Al (CH3COO)3It is dissolved into the deionized water solution of organic surface ligand GSH, by drop
Plus NaOH solution regulation PH to 6.5, obtain Al:Zn sources precursor solution；
C) container that will fill the precursor solution obtained in b is positioned in microwave reaction device, is then vacuumized
20min, then inert gas is passed through, hereafter, the precursor solution of Se is injected into Al:In the precursor solution of Zn sources, using microwave
Heating, is heated to 85 DEG C, is incubated 2h；
D) reaction temperature is down to room temperature, reinjects Zn (CH3COO)2With the GSH aqueous solution, then 85 DEG C are warming up to, insulation
60min；
E) reaction temperature is down to 55 DEG C, the PH of reaction solution is adjusted to 12, be warming up to 80 DEG C and be subsequently adding Na2S water
Solution, after insulation 60min, is cooled to room temperature, obtains Al:The quantum dot of ZnSe/ZnSe/ZnS core shell structures, takes the component such as a small amount of
The quantum dot that obtains of different soaking times carry out optical performance test；
F) quantum dot solution of gained washed, be centrifuged, obtained quantum dot powder；
Wherein, the Al that various concentrations are obtained:The optical property of ZnSe/ZnSe/ZnS quantum dots lists table 9 in.
The Al of table 9:The influence of ZnSe/ZnSe/ZnS quantum dot optical properties
Further, M:ZnSe/ZnSe/ZnS structure quantum point ink-manufacturing methods：
G) quantum dot of gained is distributed to by isopropanol, ethanol, ethylene glycol and deionized water according to volume ratio 1:1:1:1
In the solvent of composition, Al is formed:ZnSe/ZnSe/ZnS quantum dot inks.
Claims (4)
1.M:ZnSe/ZnSe/ZnS structure quantum point preparation methods, it is characterised in that the described method comprises the following steps：
（1）Under an inert atmosphere, selenium powder Se and sodium borohydride NaBH4Deionized water is dissolved in, Se sources precursor solution is obtained；
（2）Zinc acetate Zn (CH3COO)2With Doped ions Cu2+、Mn2+、Al3+Deionization of the dissolving metal salts to organic surface ligand
The aqueous solution, recycles NaOH NaOH to adjust solution PH to 6 ~ 7, obtains metal ions M:Zn precursor solutions；
（3）Metal ions M:Zn precursor solutions are placed in microwave reaction device, carry out vacuumizing 10~40 min, are passed through afterwards
Inert gas, is then injected into metal ions M by the precursor solution of Se:In Zn precursor solutions, using heating using microwave, will be anti-
Answer solution to be heated to 75 ~ 95oC from room temperature, be incubated 1~3h；
（4）Reaction temperature is down to room temperature, Zn (CH are then injected into3COO)2With the deionized water solution of organic surface ligand, then rise
Temperature is incubated 30~90min to 75 ~ 95 oC；
（5）Reaction temperature is down to 50~60 oC, afterwards using the PH of NaOH regulation reaction solutions to 11~13, then is warming up to
70~85 oC, now inject Na in reaction solution2S deionized water solutions, after 30~90min of insulation, are cooled to room temperature, obtain
Obtain M:The quantum dot solution of ZnSe/ZnSe/ZnS three-layer nuclear shell structures；
（6）The quantum dot solution of gained is washed, is centrifuged and dried, quantum dot powder is obtained；
Wherein, the M includes Cu, Mn, Al；
M in metal ion precursor solution:The mol ratio of Zn is 1:30~1:5；
Se sources precursor solution：Metal ions M:Zn precursor solutions：Zinc source：The molar concentration rate of sodium sulfide solution is 1:0.5:
1:0.5；
The molar concentration rate of the metal ion and organic surface ligand solution is 1：9~10.
2. M as claimed in claim 1:ZnSe/ZnSe/ZnS structure quantum point preparation methods, it is characterised in that Se sources presoma
Solution, metal ions M:Zn precursor solutions, zinc source, the molar concentration of sodium sulfide solution are 0.02~0.1 M；Organic table
The molar concentration of face ligand solution is 0.2~0.9 M.
3. M as claimed in claim 1:ZnSe/ZnSe/ZnS structure quantum point preparation methods, it is characterised in that organic table
Face part includes 3- mercaptopropionic acids, TGA, glutathione or cysteine.
4. a kind of quantum dot printing ink preparation method, it is characterised in that obtained by being prepared using claim 1-3 either method
M:ZnSe/ZnSe/ZnS structure quantum points prepare printing ink, by the M:ZnSe/ZnSe/ZnS structure quantum points be distributed to by
Isopropanol, ethanol, ethylene glycol and deionized water are according to volume ratio 1:1:1:In the solvent of 1 composition, formation molar concentration 0.05~
The M of 0.5M:ZnSe/ZnSe/ZnS quantum dot inks.
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| US11566345B2 (en) | 2018-02-21 | 2023-01-31 | Samsung Electronics Co., Ltd. | Cadmium-free semiconductor nanocrystal particles having high quantum efficiency, production methods thereof, and devices including the same |
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| CN111562246A (en) * | 2020-06-29 | 2020-08-21 | 中南林业科技大学 | Light irradiation Mn: ZnSe @ ZnS quantum dot photoelectric sensor and preparation method and application thereof |
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